Phthalocyanine sulfonamidopyridines



Patented Jan. 18, 1949 UNITED STAT Es PATENT OFFICE 2 459 771Pn'rnALocYAmni: sULreoNAM!!! ol PYRIDINES r Arthur L. Fox, Easton, Pa.,assignor to General Aniline & Film Corporation, New York, N.

corporation of Delaware so Drawing. Application July 11,1945,'; SerialNo. 604,513 r z 'Claims. (01. 260-3145) This invention relates to newphthalocyanine derivatives. I

The term phthalocyaninef is used herein in the generic sense to definetetraazaporphinsin which each of the four pyrrole nuclei is fused to anaromatic nucleus, e. g., phenyl, biphenyl, naphthyl, anthranyl, etc., ofwhich phthalocyanlne itself (tetrabenzotetraazaporphin) is a well-knownex-, ample. The phthaloc-yanine molecule may be metal free or contain ametal in complex combination, for example, copper, cobalt, nickel; iron,aluminum, etc. v f

It is an object of the present invention to provide new phthalocyaninesulfonamides, A further object is the provision of a process for themanufacture of the newphthalocyanine sulfonamides.

I have found that the above and other objects of the invention may beaccomplished by reacting a phthalocyanine sulfonylchloride with areactive amino group contained on or in a heterocyclic nucleus. Theheterocyclic nuclei are capable of imparting valuable characteristics tothe resulting phthalocyanine sulfonamides as will become evident as thedescription proceeds.

Any heterocyclic compound which contains in the molecule an amino groupbearing at least one free hydrogen atom may be employed forthepreparation of the compounds of the present invention. Thus,substitutedsulfonamides of the phthalocyanines may be preparedwith"heterocyclic amines such as aminotetrahydrofuran, aminopyrazine,aminothiazole, 2 amino 6 ethoxy-benzothiazole, aminothiophene, ,2-, 3:,or 4- aminopyridine, etc., or-wi th, those in which the amino group isincorporated in the ring; forexample, piperidine, methyl piperidine,piperazine, tetrahydroquinoline, morpholine, et c., or with those inwhich the amino portion is neither attached to nor is contained in theheterocyclic ring but is attached to an additional group forming part ofthemolecule of the heterocylic amine, for example, 1 (3 aminophenyl)-3-methyl-5- pyrazolone.

The preparation of the new sulionamides from the phthalocyaninesulfonylchloride and the heterocyclic amine may be carried out atelevated temperature, but preferably is conducted at room or even lowertemperatures. The reactions may be carried out in aqueous solution orsuspension, in the presence of an organic solvent such as alcohol,acetone, nitrobenzene, etc, as may be found? most suitable, or in someinstances in the complete absence of a diluent.

The new compounds are phthalocyanines containing attached to the arylenenucleiat leastone sulfona'mide group which is substituted by theheterocyclic residuerof'the starting amine. The number of these sulfonamide groups may vary. from one to four orv moreidepending' onthenumber of sulfonylchloride groups presenton' the arylene nuclei of thestarting phthalocyanine', In some instances the products may alsocontain. at'-. tached to the arylen hucleijone or more sulfonic acidgroups, either free oras the amine salt, not all the sulfonylchloridegroups bein converted in the reaction to sulfon'amide groups, orothersubstitutents such as halogen atoms, e.' g.,' chlorine, or amino orcarboxy groups, etc, ,j

Depending upon thenature ofthe heterocycli c residue present in thesulionamidej groups, the new products will v, vary in their properties,"For examplejitis possible to prepare watersoluble phthalocyaninederivatives'by incorporating on the arylene nuclei isulfonamide groupsderived from such heterocyclie .water-rsolubilizing, groups as]morpholine and zeamiriopyridinej the other hand, phthalocyanine;sulfonamides which are relatively insoluble in both aqueous solutionsandorganic solvents maybepreparedlby t e oi.,6 aminoquinoline or 2-amino-6-"ethoxy nz; thiazole. Again, others of the derivatives, iron asthat, obtained from ,piperid ine 1 and copper phthalocyanihetetrasulfonylchloride 'will be quite soluble in certainj'org'anicsolvents "'such as'ac'etone, alcohol, pyridine, .etc.Addition'allyysulfonfamide derivatives ofthe phthalocyanines may' bepreparedwhich due to-their heter'ocyclie nucleus are capable of couplingwith various di a zoniui n'.

salts to yielddiazo dyes possessing'valuable"dye ing propertiestowardscertain fibers. 0f this particular type may bementioned thoseprepared from 1-(3'-amlnopheny1) 3-.-methyl 5.- yrite- ]one".

A The new phthalocyanine colors are of a brilliant blue to greenish-blueshade and are capable of dyeing various textile fibers such as cotton,

wool and silk. Where the molecule additionally contains sulfonic acidgroups, either free or in the form of the amine salt, they are capableof being converted into color lakes with, for example, calcium or bariumsalts. Certain of these new sul fonamides are eminently suited for thecoloring of Writing inks, for example, the sulfonamides from thetetrasulfonylchloride of copper phthalocyanine, on the one hand, and2-aminopyridine, morpholine or piperidine on the other, the dyestuffsbeing employed for this purpose in the form of their soluble salts,particularly, sodium, potassium, ammonium and lithium. A furthercharcoolinaitheiresi'due I 'u'mcs of 10% hydrochloric acid'and' theprecipi- 3 acteristic of these ink colors is their stability in diluteaqueous caustic alkali solutions over relatively long periods of time, aproperty rendering themparticularly suited for coloring of writing inksrendered quick drying by a small content of caustic alkali, e..'g.,caustic soda. 'A s calors in -such-quick'drying :inka'ithey areiquiteresistant to leaching by water and characterized by their .1 light-iastness and outstanding brightness. g The starting phthalocyanine sulfonyl chlorides employed in the preparation of the plrthalocra-j nine"sulfonamides may be obtained by reacting gfachlorosulfonic acid withthe corresponding plithalocyanines at an elevated ifiemperiartim asdescribed in U. S. P. 2,219,330. They may also be sulfonic'acids ortheir salts by tre'atment w ith phosphorus pentachloride.

The invention is further illustrated by the-fol lowing specific examplesto which, however, it is not be lim'lted. Parts are by wzeightmnrrlessantherw isemeited. Y 1

' Emmpte 1. v

Ten parts of copper phthalocyanine "tetrasulfonylchlorlde is slowlystirred into a solution of 10 parts of Z-amincipyridin'ein-IDOT partsofi'nitrobenzene and the resulting mixture stirred for 10 1! hours atroom temperature, nitrobenacne is then removed from the reaction mixtureby means of a steam distillation.and'thexresulting solution evaporatedto La syrupy. residue.

tate rflltered and dried." Abriight blue Idyestuil'. is

obtained whichis .quitesoluble; in ,;dilute aqueous caustic alkali; andcontains attached to the phenyilene nuclei between three ,andgfo'ursulfonamidopyridinegroups. v a 2 r LTen parts of copper phthalocyanine'1 tetra sulfcnylchloride is stirredinto a.'so1ution of 6 parts of f1 (3"aminoph'enyli' '-'3 -:methyl-.-;pyraz o1onef and 5.5 parts of sodiumacetatein'BO parts of acetone. The. mixture is thenstirredf'at' roomtemperature .until' the reaction is complete whereupon the acetone isevaporated, and the resuiting powder stirredfinto I00. volumes; of Iwater and the resulting solution acidified fby ineanspf110%,hydmcli1or'ic acid. The resultingjprecipitate is filtered anddried. .-A'bluis hfi-[gi;een p wder [is obtained which is also, quitesoluble in dilute aqueous causticalkali.1. Itisiurthermore capable oicoupling with diazo, salts 'to iormfyalu'able dyes. i Exa pl A Ellenparts iof copperphthalocyanine itetra-sul fonylchloride is stirred into50 parts of water in 1 5 made from the corresponding phthalowanine L'Icn parts .gf 2-amino 6-ethoxybenzthiazole, 10 of copper phthalocyam'netetrasulfonylchloride and 5 parts of sodium carbonate is stirred into"100 parts of nitrobenzene. This miximne is when heated to 60 C. withefficient stir- "rin and than permitted to cool gradually back ,to roomtemperature. Stirring is continued for 110 .112 hours at roomtemperature whereupon the Lin mixture is acidified with 10% hydrochloricacid, *iiltere'da'nd dried. A dark blue powder is thus obtained.

- 1 "Example 5;

h Ten partsoi copper phthalocyanine tetrasul fonylclil lideis stirredinto alsoluti on of; lO parts of piperidine in 100 parts otmethanol and'stira' ring continued at. room temperature f or selv a]: hours untilthe reaction isicomplete. The metha nol is then removed byheating'on asteam bath and the residue stirred into 200. volumes .of water Theresulting water-insoluble precipitate is 1115; tered and dried.AbIuepoWder is obtained whi' 1 is soluble in acetone, methanol, ethanolandother organic solvents. v j' As various other embodiments of theinvention will occur .to those sk'illedln the art, it is' not i'n tendedthatthe scopeof the patent be limited except as is required by the priorart and the apg, pended claims. a i

Iclaim: a '1. copper phthalocyanine vcoritaining.fa'fttached to the,phenylene nuclei between three and. icon;

Number [Dart-e, J

496,663 Cjireat Britain ec..5, 1'3}i 520,199. Great Britainun Apr.l.7,.194Q 208,955 Switzerland June 1, i940

